JP5330070B2 - Plastic laminate and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve the adhesiveness and scratch resistance of a plasma CVD film. <P>SOLUTION: A plastic laminate is formed by successively laminating an acrylic resin thermosetting film, a thermosetting film of an organosiloxane resin, and the plasma CVD film of an organic silicon compound on at least one side of a plastic substrate. The CVD film consists of a gradient zone, in which the abundance ratio (O/Si) of oxygen atoms to silicon atoms increases in a gradient manner from the boundary surface with the thermosetting film of the organosiloxane resin, and a subsequent flat zone in which the abundance ratio (O/Si) is nearly constant. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a transparent or translucent plastic laminate having a dry hard coat layer on the surface, and a method for producing the same. More specifically, for example, the present invention relates to a plastic laminate that is used as a substitute for automobile glass and has a plasma CVD film formed by plasma CVD of an organic silicon compound containing at least carbon on the outer surface.

  For example, highly transparent plastic substrates are superior to glass in terms of lightness, impact resistance, and processability. Taking advantage of these advantages, they are widely used in place of glass as lenses for glasses and automobile windows. It has been. In such an optical application, since high importance is attached to high transparency, it is naturally required that the surface is not easily damaged. However, since the surface of a transparent plastic substrate is generally inferior in scratch resistance to glass due to its physical properties, transparent plastic laminates produced by various surface curing methods have been proposed to compensate for the drawbacks. .

For the purpose of improving the abrasion resistance of plastic moldings, for example, a method of wet coating an acrylic resin layer on the surface of a plastic molding and further wet coating a cured film of an organosiloxane resin thereon is known. For example, a coating composition in which colloidal silica is added to a condensate of alkyltrialkoxysilane and tetraalkoxysilane colloidal silica has been described (see, for example, Patent Documents 1 to 3, 5, and 6).
However, it is difficult to obtain a sufficient hardness and scratch resistance in order to use such a wet coating as a substitute for automobile glass, for example.
Also, a method of depositing aluminum oxide or silicon oxide by electron beam heating, allowing vapor deposition particles to pass through a plasma generated between the evaporation source and the substrate, increasing the kinetic energy of the vapor deposition particles, and then depositing on the substrate. (HAD process) has been proposed (see, for example, Non-Patent Documents 1 and 2). Further, a method of depositing an organic silicon-based oxidation polymer on a resin substrate by plasma polymerization in the presence of an organic silicon compound vapor such as organosiloxane, organosilane, or silazane and oxygen gas has been proposed (for example, (See Patent Document 4).

On the other hand, the present applicant, in Patent Document 7, for example, directly forming a hard coat layer by plasma polymerization in the presence of oxygen gas together with the vapor of organosiloxane, organosilane or silazane directly on the polycarbonate resin surface, It has been proposed to obtain sufficient hardness and scratch resistance, and its effectiveness has been confirmed. In the plasma polymerization method, an organic compound having a vapor pressure that exists as a gas in a vacuum reaction vessel is polymerized by plasma excitation in the vacuum reaction vessel to form a film free from defects such as pinholes. Is to use what is done. Further, the reaction in the plasma polymerization method in the vacuum reaction vessel is a reaction at normal temperature, and has an advantage that a film can be formed at a temperature lower than the durable temperature of the plastic. Moreover, although the reaction in this plasma polymerization method is performed at a relatively low temperature, since the electron temperature is high, a reaction that occurs only at a high temperature in a chemical reaction can be performed, so the degree of crosslinking is high, There is an advantage that a film having high hardness can be formed.
However, for example, a plastic substrate such as a polycarbonate resin remains a major problem in that it may be deteriorated by being exposed to ultraviolet rays, particularly in an automobile application.
One solution for this is to block out ultraviolet radiation. Therefore, Patent Document 8 discloses that an ultraviolet blocking coating layer is formed on the polycarbonate resin surface, and an abrasion resistant coating layer is formed thereon. The abrasion-resistant coating layer in Patent Document 8 is composed of “a specific diorganodiorganooxysilane, a specific organotriorganooxysilane, and both of these”. Although it is described that it can be formed by a legal method, no further detailed explanation is given. In addition, in the case of Patent Document 8, it cannot be estimated that the adhesion between the ultraviolet blocking coating layer and the wear resistant coating layer is high.
Moreover, when forming a dry hard-coat layer like patent document 7 directly on the polycarbonate resin surface, it is difficult to make adhesiveness high.

Japanese Unexamined Patent Publication No. Sho 63-27879 Japanese Patent Laid-Open No. 01-306476 JP 2000-318106 A Japanese Patent Laid-Open No. 08-27289 Japanese Examined Patent Publication No. 4-55615 JP 2004-35608 A Japanese Patent No. 3446150 JP 2005-519792

M.M. Krug, “Abrasion resisting coatings on plastic by PVD high rate deposition”, Proceedings of the 3rd-ICCG 2000, p577. SUZUKI Takuichi et al., “Surface Treatment Technology Forefront Report (4) Fraunhofer Electron Beam Plasma Laboratory (III)”, Industrial Materials, Vol. 49No. 7 P72 (July 2001 issue)

Therefore, the main object of the present invention is to obtain a transparent or translucent plastic laminate in which the dry hard coat layer on the surface has high adhesion to the plastic substrate.
Another object is to obtain a transparent or translucent plastic laminate that is excellent in weather resistance (ultraviolet ray blocking, etc.) and has high adhesion of the dry hard coat layer on the surface to the plastic substrate.
Further problems will become clear from the following description.

The present invention that has solved the above problems is as follows.
<Invention of Claim 1>
Acrylic resin thermosetting film, organosiloxane resin thermosetting film and organosilicon compound plasma CVD film are sequentially laminated on at least one surface of a plastic substrate,
The CVD film has an inclined zone in which the abundance ratio (O / Si ratio) between oxygen atoms and silicon atoms increases from the interface with the thermosetting film of the organosiloxane resin, followed by a substantially constant flat zone. Ri consists of,
A plastic laminate having a thickness of an inclined zone of the CVD film of 0.1 to 1 μm .

(Function and effect)
When an acrylic resin thermosetting film or organosiloxane resin thermosetting film is laminated on at least one side of a plastic substrate by wet, and when a CVD film is further laminated, the O / Si ratio is changed near the interface of the CVD film. Thus, the adhesion between the wet layer and the CVD layer is excellent.
Furthermore, in order to make the surface layer of the CVD layer have a high hardness in order to ensure scratch resistance, the O / Si ratio in the CVD film is continuously changed. By providing an inclined zone that ensures adhesion between the wet film and the CVD film, and a flat zone for achieving hardness on the surface of the CVD film, both excellent adhesion within the single layer and high hardness are achieved. Can be achieved.

Further, the O / Si ratio of the CVD film is 0. 0 from the contact surface with the wet layer toward the outer surface side of the CVD layer. By continuously increasing the thickness in the range of 1 to 1 μm , it is possible to ensure suitable adhesion of the CVD layer to the wet layer.

<Invention of Claim 2 >
The plastic laminate according to claim 1, wherein the flat zone of the CVD film has an O / Si ratio of 1.4 or more and less than 2.

(Function and effect)
When the O / Si ratio is 1.4 or more and less than 2 on the surface of the CVD film, it is possible to achieve a hardness exhibiting sufficient scratch resistance.

<Invention of Claim 3 >
The CVD film is a film obtained by plasma polymerization in the presence of vapor and oxygen gas of at least one organic silicon compound selected from the group consisting of compounds consisting of organosiloxane, organosilane and silazane. 3. The plastic laminate according to 1 or 2 .

(Function and effect)
As the plasma CVD layer, a film obtained by plasma polymerization in the presence of oxygen gas together with at least one organosilicon compound vapor selected from the group consisting of at least one organosiloxane, organosilane, and silazane is sufficiently adhered. A plastic laminate exhibiting properties, hardness and scratch resistance can be obtained.

<Invention of Claim 4 >
The plastic laminate according to any one of claims 1 to 3 , wherein the plastic substrate is a transparent or translucent resin.

(Function and effect)
By using a transparent or translucent resin for the substrate, it is possible to utilize the excellent mechanical strength and optical characteristics of the substrate itself, and to improve the scratch resistance and weather resistance of the substrate.

<Invention of Claim 5 >
At least on one side of a plastic substrate, a step of wet-coating acrylic resin and thermosetting, a step of wet-coating organosiloxane resin and thermosetting, and at least selected from the group consisting of compounds consisting of organosiloxane, organosilane and silazane Including the step of forming a film by plasma polymerization in the presence of vapor of one kind of organosilicon compound and oxygen gas in the coexistence,
The plasma polymerization comprising an inclined zone in which an abundance ratio of oxygen atoms to silicon atoms (O / Si ratio) increases gradually from the interface with the thermosetting film of the organosiloxane resin, followed by a substantially constant flat zone. Produce a membrane ,
Method for producing a plastic laminate according to claim 0.1~1μm and to Rukoto the thickness of the inclined zone of the CVD film.

(Function and effect)
The same effects as those of the first aspect of the invention can be achieved.

  According to the present invention, it is possible to obtain a transparent or translucent plastic laminate in which the adhesion of the dry hard coat layer on the surface to the plastic substrate is high. For example, it is possible to obtain a transparent or translucent plastic laminate that is excellent in weather resistance (such as ultraviolet blocking) and has high adhesion of the dry hard coat layer on the surface to the plastic substrate.

It is sectional drawing of the transparent or translucent plastic laminated body applied to one Embodiment of this invention. It is a graph which shows typically the change of the abundance ratio (O / Si ratio) of an oxygen atom and a silicon atom from the surface of a plastic substrate to the outer surface of a film. It is a graph which shows typically a time-dependent change of input RF electric power, organosilicon compound vapor, and supply rate of oxygen gas as plasma polymerization reaction conditions in an example. It is a graph which shows typically a time-dependent change of input RF electric power, organosilicon compound vapor, and supply rate of oxygen gas as plasma polymerization reaction conditions in a comparative example. It is the schematic of the example of the capacitive coupling type plasma polymerization apparatus for forming the plasma CVD film | membrane of this invention.

Hereinafter, an embodiment of a transparent or translucent plastic laminate according to the present invention will be described in detail with reference to the accompanying drawings.
As shown in FIG. 1, a transparent or translucent plastic laminate 100 according to the present invention has a thermosetting acrylic resin film 60, an organosiloxane resin thermosetting film 70, and a plasma CVD film 80 on the surface of a plastic substrate 50. And are stacked in order.

<Plastic substrate 50>
Specific examples of the plastic substrate material 50 include polycarbonate resin, acrylic resin such as polymethyl methacrylate, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, poly (ethylene-2,6-naphthalate), polystyrene, polypropylene, poly Examples include arylate and polyethersulfone. These resins can be used alone or in admixture of two or more.

  As the base material having adhesion with the first layer and excellent wear resistance, a polycarbonate resin and an acrylic resin are preferable, and a polycarbonate resin is particularly preferable.

  The polycarbonate resin is, for example, a polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melting method. Representative examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4 -Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxy) Phenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. However, bisphenol A is preferred. These divalent phenols can be used alone or in admixture of two or more.

  As the polycarbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing polycarbonate resin by reacting dihydric phenol and carbonate precursor by interfacial polycondensation method or melting method, catalyst, terminal terminator, dihydric phenol antioxidant, etc. are added as necessary. May be used. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

The molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 15,000 to 35,000 in terms of viscosity average molecular weight (M). A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength is obtained and the melt fluidity during molding is good. The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

Such polycarbonate resins include stabilizers such as phosphites, phosphates, and phosphonates as necessary, tetrabromobisphenol A, low molecular weight polycarbonate of tetrabromobisphenol A, flame retardants such as decabromodiphenol, and colorants. Further, other resins such as a lubricant, the above-described polyester resin and ABS can be added.
The thickness of the plastic substrate is preferably in the range of 1 to 30 mm.

<Thermosetting acrylic resin film 60>
The thermosetting acrylic resin film 60 is a film obtained by thermosetting an acrylic resin composition. The acrylic resin composition contains (A) an acrylic copolymer, (B) a crosslinking agent, and (C) a curing catalyst. The components (A) to (C) will be described in detail.

(Acrylic copolymer (A))
The acrylic copolymer (hereinafter sometimes referred to as component (A)) is an acrylic copolymer containing at least 70 mol% of a repeating unit represented by the following formula (A).

  In the formula, X is a hydrogen atom or a methyl group. In X, the proportion of hydrogen atoms is 30 mol% or less. Y is a methyl group, an ethyl group, a cycloalkyl group, a hydroxyalkyl group having 2 to 5 carbon atoms, or an ultraviolet absorber residue. In Y, the ratio of a cycloalkyl group is 0-85 mol%. The ratio of the ultraviolet absorber residue is 0 to 15 mol%, and the total ratio of methyl group and ethyl group is 1 to 98 mol%.

  The acrylic copolymer preferably contains a repeating unit represented by the following formulas (A-1), (A-2), (A-3) and (A-4).

((A-1) unit)

In formula (A-1), Y ¹ represents a methyl group or an ethyl group. The repeating unit represented by the formula (A-1) is obtained by polymerizing methyl methacrylate and ethyl methacrylate. These can be used alone or in combination. The content of the formula (A-1) unit in the acrylic copolymer is preferably 1 to 98 mol%. When the proportion of (A-1) units is less than 1 mol%, the flexibility of the first layer is lowered and cracks are likely to occur in the second layer. Moreover, since adhesiveness with a base material or a 2nd layer falls, it is unpreferable.

((A-2) units)

In formula (A-2), X ¹ is a hydrogen atom or a methyl group, and Y ² is a cycloalkyl group. The repeating unit represented by the formula (A-2) is obtained by polymerizing acrylate or methacrylate having at least one cycloalkyl group in the molecule. The cycloalkyl group preferably has 5 to 12 carbon atoms. Specific examples include a cyclohexyl group and a cyclooctyl group.

  The repeating unit represented by (A-2) can be introduced by copolymerizing a corresponding monomer. Specific examples of the corresponding monomer include cyclohexyl acrylate, 4-methylcyclohexyl acrylate, 2,4-dimethylcyclohexyl acrylate, 2,4,6-trimethylcyclohexyl acrylate, 4-t-butylcyclohexyl acrylate, adamantyl acrylate, dicyclopentadi Enyl acrylate, cyclohexyl methyl acrylate, 4-methyl cyclohexyl methyl acrylate, 2,4-dimethyl cyclohexyl methyl acrylate, 2,4,6-trimethyl cyclohexyl methyl acrylate, 4-t-butyl cyclohexyl methyl acrylate, cyclohexyl methacrylate, 4-methyl cyclohexyl Methacrylate, 2,4-dimethylcyclohexyl methacrylate, 2,4,6-trimethyl Cyclohexyl methacrylate, 4-t-butylcyclohexyl methacrylate, adamantyl methacrylate, dicyclopentadienyl methacrylate, cyclohexylmethyl methacrylate, 4-methylcyclohexylmethyl methacrylate, 2,4-dimethylcyclohexylmethyl methacrylate, 2,4,6-trimethylcyclohexyl Examples thereof include compounds such as methyl methacrylate and 4-t-butylcyclohexylmethyl methacrylate. These can be used alone or in admixture of two or more. Of these, cyclohexyl methacrylate is preferably employed.

  The content of the (A-2) unit in the acrylic copolymer is preferably 1 to 85 mol%. When the proportion of the unit (A-2) is less than 1 mol%, the dispersibility of the triazine-based ultraviolet absorber is lowered and the first layer is likely to be whitened. The adhesiveness of is reduced.

((A-3) units)

In formula (A-3), X ² is a hydrogen atom or a methyl group, and Y ³ is an alkylene group having 2 to 5 carbon atoms. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group. The unit (A-3) has a hydroxy group.

  The unit (A-3) can be introduced by copolymerizing a corresponding monomer. Specific examples of the corresponding monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, Examples include 4-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, and 2-hydroxybutyl methacrylate. These can be used alone or in admixture of two or more. Of these, 2-hydroxyethyl methacrylate is preferably employed.

  The content of the (A-3) unit in the acrylic copolymer is preferably 1 to 15 mol%, more preferably 5 to 15 mol%. (A-3) When the ratio of the unit exceeds the above range, cracks are likely to occur in the coating layer, which is not preferable.

((A-4) units)

In formula (A-4), X ³ is a hydrogen atom or a methyl group, and Y ⁴ is an ultraviolet absorber residue, preferably a triazine-based ultraviolet absorber residue. The unit (A-4) can be introduced by copolymerizing an acrylate or methacrylate monomer having an ultraviolet absorber residue. Specific examples of the acrylate or methacrylate monomer having an ultraviolet absorber residue include repeating units derived from an acrylic monomer represented by the following formula (A-4-a) or formula (A-4-b). Preferably used.

（式（Ａ−４−ａ）中Ｒ¹¹は炭素数２〜６のアルキレン基であり、Ｒ¹²は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ¹³、Ｒ¹⁴は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ¹⁵は炭素数１〜１８のアルキル基を表し、Ｘ⁴は水素原子またはメチル基であり、Ｖ¹は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

(In formula (A-4-a), R ¹¹ represents an alkylene group having 2 to 6 carbon atoms, R ¹² represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, R ¹³ and R ¹⁴ are the same or independent of each other, and are substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, or a halogen atom. Represents an optionally substituted phenyl group, R ¹⁵ represents an alkyl group having 1 to 18 carbon atoms, X ⁴ represents a hydrogen atom or a methyl group, V ¹ represents a hydrogen atom, OH group or 1 to 12 carbon atoms. Represents an alkyl group.)

（式（Ａ−４−ｂ）中Ｒ¹⁶は水素原子、炭素数１〜１８のアルキル基または炭素数１〜１８のアルコキシ基を表し、Ｒ¹⁷、Ｒ¹⁸は同一または互いに独立して水素原子、ハロゲン原子、炭素数１〜１８のアルキル基、炭素数１〜１８のアルコキシ基、または炭素数１〜１８のアルキル基もしくはハロゲン原子で置換されていてもよいフェニル基を表し、Ｒ¹⁹は炭素数１〜１８のアルキル基を表し、Ｘ⁵は水素原子またはメチル基であり、Ｖ²は水素原子、ＯＨ基または炭素数１〜１２のアルキル基を表す。）

(In the formula (A-4-b), R ¹⁶ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms, and R ¹⁷ and R ¹⁸ are the same or independent from each other. , A halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 18 carbon atoms or a halogen atom, and R ¹⁹ is carbon. represents the number 1 to 18 alkyl group, X ⁵ is a hydrogen atom or a methyl group, V ² represents a hydrogen atom, OH group or an alkyl group having 1 to 12 carbon atoms.)

  In the present invention, the ultraviolet absorbent residue is a residue of an ultraviolet absorbent and has ultraviolet absorbing performance. For example, since the triazine-based ultraviolet absorbent residue is partially bonded to the acrylic copolymer by lacking a part of the terminal of the triazine compound, the molecular weight is strictly different between the residue and the triazine compound. However, since the weight of the missing portion is small compared to the whole, the present invention assumes that the weight of the residue and the weight of the triazine compound are the same for the sake of convenience.

  The content of the (A-4) unit in the acrylic copolymer is preferably 0 to 15 mol%, more preferably 0 to 10 mol%, still more preferably 0 to 7 mol%. When the proportion of (A-4) units exceeds 15 mol%, the adhesion between the substrate and the first layer, the first layer and the second layer is lowered, and cracks are likely to occur in the second layer. The total content of the triazine-based ultraviolet absorbent residue in formula (A-4) and the component (D) described later is preferably 1 to 40% by weight, more preferably 2 to 30% by weight.

  The total content of the repeating units represented by the formulas (A-1) to (A-4) in the acrylic copolymer is at least 70 mol%, preferably 80 to 100 mol%, more preferably 90 to 100 mol. %. The acrylic copolymer is preferably 1-98 mol% of formula (A-1), 1-85 mol% of formula (A-2), 1-15 mol% of formula (A-3) and 0-15. Containing mol% units of formula (A-4).

((A-5) units)
The acrylic copolymer preferably further contains a repeating unit represented by the following formula (A-5). (A-5) Weather resistance improves by containing a unit.

In the formula, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an alkoxy group.
R ¹⁰ is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  The proportion of the unit (A-5) is preferably 0.1 to 15 mol%, more preferably 0.1 to 10 mol%, still more preferably 1 to 8 in 100 mol% of all repeating units of the acrylic copolymer. Mol%. If it exceeds 15 mol%, the adhesion to the substrate and the second layer tends to be lowered.

  By including the unit (A-5), radical scavenging ability can be imparted, and weather resistance can be further improved. The total of (A-1) units to (A-5) units is at least 70 mol%, more preferably at least 80 mol%, and even more preferably at least 90 mol% in 100 mol% of all repeating units of the acrylic copolymer. is there.

(Other units)
The acrylic copolymer (component (A)) containing the units (A-1) to (A-5) may further contain other repeating units for imparting functionality or the like. The other repeating unit is 30 mol% or less, preferably 20 mol% or less, particularly preferably 10 mol% or less, based on 100 mol% of all repeating units of the acrylic copolymer of component (A).

  Other repeating units can be introduced by copolymerizing vinyl monomers copolymerizable with acrylate or methacrylate monomers. Other vinyl monomers include acrylic acid, methacrylic acid, acrylic acid amide, methacrylic acid amide, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, in terms of durability such as adhesion or weather resistance. Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2- (2′-hydroxy-5′-acryloxyethylphenyl) benzotriazole, 2- (2′-hydroxy-5′- Acryloxyethoxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-acryloxypropylphenyl) benzotriazole, 2- (2′-hydroxy-5′-acryloxypropoxyphene) ) Benzotriazole, 2- (2'-hydroxy-5'-acryloxyethylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-acryloxyethyl-5'-) t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-acryloxyethyl-5′-t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4- (acryl Roxyethoxy) benzophenone, 2-hydroxy-4- (acryloxypropoxy) benzophenone, 2,2′-dihydroxy-4- (acryloxyethoxy) benzophenone, 2-hydroxy-4- (acryloyloxyethyl) benzophenone, 2- ( 2'-hydroxy-5'-methacryloxyethylphenyl) benzotriazole, 2- (2'- Droxy-5′-methacryloxyethoxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-methacryloxypropylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methacryloxypropoxyphenyl) Benzotriazole, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-methacryloxyethyl-5′-t-butylphenyl) Benzotriazole, 2- (2′-hydroxy-3′-methacryloxyethyl-5′-t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4- (methacryloxyethoxy) benzophenone, 2-hydroxy- 4- (methacryloxypropoxy) benzophenone, 2,2 Examples include '-dihydroxy-4- (methacryloxyethoxy) benzophenone and 2-hydroxy-4- (methacryloyloxyethyl) benzophenone, and these can be used alone or in combination of two or more. Moreover, it is not necessary to use an acrylic resin having a single composition alone, and two or more kinds of acrylic resins may be mixed and used.

  The molecular weight of the acrylic copolymer (A) is preferably 20,000 or more, more preferably 50,000 or more in terms of weight average molecular weight. Further, those having a weight average molecular weight of 10 million or less are preferably used. Therefore, the weight average molecular weight of the acrylic copolymer is preferably 50,000 to 10,000,000, more preferably 50,000 to 1,000,000, and even more preferably 50,000 to 500,000. An acrylic copolymer having such a molecular weight range is preferable because it exhibits sufficient performance such as adhesion and strength as the first layer.

(Crosslinking agent (B))
As the crosslinking agent for component (B), a blocked polyisocyanate compound is preferably used. The blocked polyisocyanate compound is obtained by reacting an isocyanate group with a blocking agent to substantially eliminate a free isocyanate group, and having no reactivity. By heating, the blocking agent is separated into an isocyanate group. It is a compound that leads to reactivity.

  (B) As an isocyanate group of a polyisocyanate compound, an oxime such as acetoxime and methyl ethyl ketoxime, an active methylene compound such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone, methanol, ethanol Block isocyanate obtained by adding a blocking agent represented by alcohols such as 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol, and phenols such as phenol, cresol and ethylphenol Compounds.

  Examples of the polyisocyanate compound to which the blocking agent is added include polyisocyanates, adducts of polyisocyanates and polyhydric alcohols, cyclized polymers of polyisocyanates, isocyanate burettes, and the like. Examples of polyisocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, hexamethylene diisocyanate, Examples include dicyclohexylmethane diisocyanate and isophorone diisocyanate.

  In component (B), an isocyanate group is generated for the first time during the thermosetting reaction, so that the coating composition is excellent in storage stability, and the isocyanate group is used in moisture in the coating composition, air, and solvent coating composition. A cured film having a stable physical property which is hardly consumed by the side reaction with the alcohol solvent and hardly affected by the coating environment can be formed. These blocked isocyanates can be used alone or in admixture of two or more.

  Of the blocked isocyanates, blocked aliphatic and / or alicyclic polyisocyanate compounds are particularly preferable because of excellent weather resistance. The blocked aliphatic and / or alicyclic polyisocyanate compound is obtained by reacting (i) a hydroxy compound having 2 to 4 hydroxy groups with an aliphatic and / or alicyclic diisocyanate compound. An adduct polyisocyanate compound obtained by blocking an adduct polyisocyanate compound with a blocking agent; and (ii) an isocyanurate obtained by blocking an isocyanurate type polyisocyanate compound derived from an aliphatic and / or alicyclic diisocyanate compound with a blocking agent. Type polyisocyanate compounds are preferred. Among them, aliphatic diisocyanate compounds and / or alicyclic diisocyanate compounds having 4 to 20 carbon atoms are preferable, and those having 4 to 15 carbon atoms are more preferable. By setting the number of carbon atoms of the isocyanate compound in such a range, a coating film having excellent durability is formed.

  The converted isocyanate group ratio is a value that represents the weight of the isocyanate group to be produced as a percentage of the weight of the component (B) when the component (B) is heated to separate the blocking agent.

  The component (B) has a converted isocyanate group ratio of 5.5 to 50% by weight, preferably 6.0 to 40% by weight, and most preferably 6.5 to 30% by weight. When the isocyanate group ratio is less than 5.5% by weight, the blended amount of the blocked polyisocyanate compound with respect to the acrylic resin increases, and the adhesion to the substrate becomes poor. On the other hand, if the isocyanate group ratio is more than 50% by weight, the flexibility of the coating layer is lowered, and the coating layer is cracked when the second layer is thermally cured, thereby impairing durability against environmental changes. The isocyanate group ratio (% by weight) is determined by a method in which an isocyanate group is ureated with a known amount of amine and excess amine is titrated with an acid.

  The content of the component (B) is 0.8 to 1.5 equivalents, preferably 0.8 to 1.3 equivalents, most preferably an isocyanate group with respect to 1 equivalent of a hydroxy group in the acrylic copolymer (A). Is an amount of 0.9 to 1.2 equivalents.

  When the hydroxy group in component (A) and the isocyanate group in component (B) form a crosslink by a urethane bond, the first layer can maintain good adhesion to the substrate and the second layer. it can. Further, the crosslink density is hardly lowered by ultraviolet rays, water, oxygen, etc., and the adhesion can be maintained for a long time. In addition, durability under a high temperature environment can be maintained. It also has excellent weather resistance.

  When the isocyanate group is less than 0.8 equivalent, the crosslinking becomes insufficient, resulting in insufficient durability in a high temperature environment, and the unreacted hydroxy group absorbs moisture to show high affinity with water molecules. Weather resistance and boiling water resistance also deteriorate. If there are more than 1.5 equivalents of isocyanate groups, the first layer will have a very high crosslink density with allophanate bonds, will be a hard and brittle layer, will be less responsive to environmental changes, and will be more adhesive to environmental changes. Inferior.

(Curing catalyst (C))
Component (C) is a curing catalyst. The curing catalyst is used for promoting dissociation of the crosslinking agent, preferably the blocking agent, of the component (B). Further, it is used for promoting the urethanization reaction between the isocyanate group formed by dissociation and the hydroxy group in the component (A).

  As the component (C), at least one compound selected from the group consisting of an organic tin compound, an organic titanium compound, an organic zirconium compound, a tertiary amine compound, and a quaternary ammonium salt compound is preferable.

Among these curing catalysts, an organotin compound is preferably used, and an organotin compound represented by the following formula (C) is particularly preferably used.
R ²⁰ _m Sn (OCOR ²¹ ) _4-m (C)

Here, R ²⁰ is a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 4 to 8 carbon atoms. R ²¹ is a substituted or unsubstituted hydrocarbon group having 1 to 17 carbon atoms, preferably a substituted or unsubstituted alkyl group having 1 to 17 carbon atoms. As the substituent, an alkyl group having 1 to 4 carbon atoms is preferable. m is an integer of 0-3.

  Typical examples of the curing catalyst include monobutyltin tris (2-ethylhexanoate), dimethyltindineodecanoate, dibutyltinbis (2-ethylhexanoate), monobutyl for organotin compounds. Tintris (n-butylpropionate), dibutyltin dilaurate, monohexyltin trioctoate, dihexyltin dioctoate, trihexyltin monooctoate, monohexyltin tris (methyl maleate), dioctyltin diacetate, trioctyl Tin monoacetate, dioctyltin bis (methyl maleate), monooctyltin tris (methylpropionate), dioctyltin dipropionate), trioctyltin monopropionate, monooctyltin trioctate, dioctyl Njiokutoeto include trioctyl tin mono-octoate. These are used individually or in mixture of 2 or more types.

  Typical examples of the organic titanium compound include alkoxy titanium compounds such as tetraisopropyl titanate, tetrabutoxy titanate, and tetraoctyl titanate, and titanium chelate compounds such as titanium acetylacetonate and titanium ethyl acetoacetate. These are used individually or in mixture of 2 or more types.

  Typical examples of organic zirconium compounds include alkoxyzirconium compounds such as tetraisopropoxyzirconium, tetrabutoxyzirconium, and tetraoctoxyzirconium, zirconium such as zirconium tetraacetylacetonate, zirconium tetraethylacetoacetate, and zirconium tributoxyacetylacetonate. Examples include chelate compounds. These are used individually or in mixture of 2 or more types.

  Representative examples of the tertiary amine compound include dimethylethanolamine, triethylenediamine, methylhydroxyethylpiperazine, dimethylaminoethoxyethanolamine and the like. These are used individually or in mixture of 2 or more types.

  Typical examples of the quaternary ammonium salt compounds include 2-hydroxyethyl, tri-n-butylammonium, 2,2-dimethylpropionate, 2-hydroxyethyl, tri-n-butylammonium, 2,2-dimethylbutane. Noeto, 2-hydroxypropyl • tri-n-butylammonium • 2,2-dimethylpropionate, 2-hydroxypropyl • trin-butylammonium • 2,2-dimethylbutanoate and the like. These are used individually or in mixture of 2 or more types.

  The content of component (C) is 0.001 to 0.4 parts by weight, preferably 0.002 to 0.3 parts by weight, based on 100 parts by weight of the total of components (A) and (B). When the content of component (C) is less than 0.001 part by weight, the effect of promoting the crosslinking reaction cannot be obtained, and when it exceeds 0.4 part by weight, the adhesion between the first layer and the second layer is lowered. It is not preferable.

(Triazine UV absorber (D))
As the component (D), a triazine-based ultraviolet absorber represented by the following formula (D) is preferably used. The component (D) is improved in dispersibility due to the cycloalkyl group in the acrylic copolymer of the component (A), and can exhibit the ultraviolet absorbing function without waste. As a result, the first layer of the present invention has excellent weather resistance.

In the formula, R ⁴ is an alkyl group having 1 to 18, preferably 3 to 16, more preferably 4 to 8 carbon atoms, a substituent represented by —CH ₂ CH (OH) CH ₂ O—R ⁸ or —CH. (CH ₃₎ represents a substituent represented by ^{C (O) O-R 9} . R ⁸ is an alkyl group having 1 to 18 carbon atoms, preferably 3 to 16 carbon atoms, more preferably 6 to 14 carbon atoms. R ⁹ is an alkyl group having 1 to 18 carbon atoms, preferably 3 to 16 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of the alkyl group for R ⁴ , R ⁸ and R ⁹ include an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

R ⁵ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Carbon number of an alkyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-4. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Carbon number of an alkoxy group becomes like this. Preferably it is 1-8, More preferably, it is 1-4. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

R ⁶ and R ⁷ may each independently be substituted with a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, or a halogen atom. Represents a phenyl group.

  Carbon number of an alkyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-4. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Carbon number of an alkoxy group becomes like this. Preferably it is 1-8, More preferably, it is 1-4. Examples of the alkoxy group include an ethoxy group, a propoxy group, and a butoxy group. The number of carbon atoms of the alkyl group substituted on the phenyl group is preferably 3 to 16, more preferably 4 to 8. Examples of the alkyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  V represents a hydrogen atom, an OH group, or an alkyl group having 1 to 12 carbon atoms. Carbon number of an alkyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-4. Examples of the alkyl group include an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

Specifically, as a triazine ultraviolet absorber represented by the formula (D), manufactured by Ciba Specialty Chemicals Co., Ltd.
(1) Tinuvin 1577 (R ⁴ is a hexyl group, R ⁵ , R ⁶ , R ⁷ and V are hydrogen atoms),
(2) Tinuvin 400 (R ⁴ is —CH ₂ CH (OH) CH ₂ O—R ⁸ (R ⁸ is a dodecyl group and a tridecyl group), R ⁵ , R ⁶ , R ⁷ and V are hydrogen atoms),
(3) Tinuvin 405 (R ⁴ is —CH ₂ CH (OH) CH ₂ O—R ⁸ (R ⁸ is an octyl group), R ⁵ , R ⁶ , R ⁷ and V are methyl groups),
(4) Tinuvin 460 (R ⁴ is a butyl group, R ⁵ , R ⁶ , R ⁷ are butyloxy groups, V is an OH group),
(5) Tinuvin 479 (R ⁴ is —CH (CH ₃ ) C (O) O—R ⁹ (R ⁹ is an octyl group) R ⁵ is a hydrogen atom, R ⁶ and R ⁷ are phenyl groups, and V is a hydrogen atom) , Etc.

  These can be used alone or in admixture of two or more. Preferably, by mixing two or more types having different maximum absorption wavelengths, ultraviolet rays can be absorbed in a wider wavelength region in the ultraviolet region, and ultraviolet rays in a wavelength region where one of the ultraviolet absorbers is weakly absorbed can be used. Further, the absorption of the other is more preferable because the durability of the ultraviolet absorber itself to UV can be improved.

  Content of these (D) components is 0-40 weight part with respect to a total of 100 weight part of (A) component and (B) component, and 0-30 weight part. When it exceeds 40 weight part, the adhesiveness of a 1st layer and a base material or a 1st layer and a 2nd layer will fall.

(solvent)
The first layer can be formed by applying an acrylic resin composition (paint) to the substrate surface. The acrylic resin composition preferably further contains a solvent.

  The solvent is preferably a solvent that does not react with the substrate and does not dissolve the substrate. Examples of such solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane, esters such as ethyl acetate and ethoxyethyl acetate, Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2- Examples include alcohols such as butoxyethanol, hydrocarbons such as n-hexane, n-heptane, isooctane, benzene, toluene, xylene, gasoline, light oil, kerosene, acetonitrile, nitromethane, water, etc. Or two or more It may be used as a mixture.

  The concentration of the resin (solid component) in the acrylic resin composition is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.

  In the present invention, the first layer can be formed by applying an acrylic resin composition (coating material) to the substrate surface, then removing the solvent by heating or the like, and further heating to cause crosslinking (thermosetting). .

  For coating the coating material on the substrate, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method is appropriately selected according to the shape of the substrate to be coated. be able to. The substrate coated with the acrylic resin composition is usually thermally cured by drying and removing the solvent at a temperature from room temperature to a temperature lower than the thermal deformation temperature of the substrate.

  The thermosetting is preferably performed at a high temperature within a range where there is no problem in the heat resistance of the base material because the curing can be completed more quickly. In addition, at normal temperature, thermosetting does not advance completely, and it does not become a coat layer having sufficient crosslink density required for the first layer. In the process of thermosetting, the crosslinkable group in the thermosetting acrylic resin composition reacts to increase the crosslink density of the coat layer, and the coat layer has excellent adhesion, boiling water resistance, and durability in a high temperature environment. It becomes.

  The thermosetting temperature is preferably 80 to 160 ° C, more preferably 100 to 140 ° C, and still more preferably 110 to 130 ° C. The heat curing time is preferably 10 minutes to 3 hours, more preferably 20 minutes to 2 hours. A cross-linked group is cross-linked by heating to obtain a laminate in which an acrylic resin layer is laminated as the first layer. When the thermosetting time is 10 minutes or less, the crosslinking reaction does not proceed sufficiently, and the first layer may have poor durability and weather resistance under a high temperature environment. Further, in view of the performance of the acrylic resin composition, the heat curing time is sufficient within 3 hours.

  By thermosetting the acrylic resin composition to form the first layer, the adhesion between the second layer and the substrate is improved, and a laminate having excellent wear resistance and weather resistance can be obtained. The film thickness of the first layer is preferably 1 to 20 μm, more preferably 2 to 10 μm. When the film thickness is less than 1 μm, the transmittance of ultraviolet rays increases, yellowing of the base material occurs, and the adhesion is lowered, resulting in poor weather resistance. If the film thickness exceeds 20 μm, the internal stress increases and the crosslinking reaction does not proceed sufficiently at the time of thermosetting, resulting in a layer having poor durability in a high temperature environment. Moreover, the volatilization of the solvent during coating of the acrylic resin composition becomes insufficient, and the solvent remains in the first layer, which impairs boiling water resistance and weather resistance.

<Thermosiloxane resin thermosetting film 70>
The organosiloxane resin thermosetting film 70 is a film obtained by thermosetting an organosiloxane resin composition. The organosiloxane resin composition contains colloidal silica (E component), a hydrolysis condensate of alkoxysilane (F component), and optionally a metal oxide (G component).

(Colloidal silica (E))
As the colloidal silica (component E), silica fine particles having a diameter of preferably 5 to 200 nm, more preferably 5 to 40 nm are dispersed in water or an organic solvent in a colloidal form.

  As such colloidal silica, specifically, as a product dispersed in an acidic aqueous solution, Snowtex O of Nissan Chemical Industry Co., Ltd., Cataloid SN30 of Catalyst Chemical Industry Co., Ltd., a product dispersed in a basic aqueous solution. SNO-TEX 30 and SNO-TEX 40 of Nissan Chemical Industries, Ltd. Cataloid S30 and Cataloid S40 of Catalyst Chemical Industry Co., Ltd. MA-ST and IPA of Nissan Chemical Industry Co., Ltd. as products dispersed in organic solvents -ST, NBA-ST, IBA-ST, EG-ST, XBA-ST, NPC-ST, DMAC-ST and the like.

  The colloidal silica can be used in either a water dispersion type or an organic solvent dispersion type, but a water dispersion type is preferably used. In the case of water-dispersed colloidal silica, there are a large number of hydroxyl groups on the surface of the silica fine particles, which are strongly bonded to the alkoxysilane hydrolysis condensate, so that a plastic laminate having more excellent wear resistance can be obtained. Conceivable. The water-dispersed colloidal silica can be used in either an acidic aqueous dispersion type or a basic aqueous dispersion type. However, the aqueous dispersion type colloidal silica is acidic in terms of diversity of selection of curing catalyst, appropriate hydrolysis of trialkoxysilane, and realization of a condensed state. An aqueous dispersion type colloidal silica is preferably used.

(Hydrolysis condensate of alkoxysilane (F))
The alkoxysilane hydrolyzed condensate (component F) is obtained by subjecting an alkoxysilane represented by the following formula (F) to a hydrolytic condensation reaction.
R ¹ _m R ² _n Si (OR ³ ) _4-mn (F)

In the formula, R ¹ and R ² are each independently one or more selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a vinyl group, or a methacryloxy group, an amino group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. It is a C1-C3 alkyl group substituted with a group. R ¹ and R ² are each independently preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.

R ³ is an alkyl group having 1 to 4 carbon atoms or a vinyl group. R ³ is preferably an alkyl group having 1 to ³ carbon atoms, particularly preferably a methyl group or an ethyl group. m and n are each independently an integer of 0, 1 or 2, and m + n is an integer of 0, 1 or 2. m and n are each preferably 0 or 1. Further, m + n is preferably 1.

  Specific examples of the alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, methyltrimethoxysilane, methyltrimethoxysilane. Ethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycine Sidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl)- γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, etc. Among them, alkyltrialkoxysilane is preferable, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferable. These can be used alone or in combination. Furthermore, in order to impart flexibility to the cured film depending on the application, it is also preferable to use a mixture of bifunctional alkoxysilanes such as dimethyldimethoxysilane.

  Moreover, it is preferable that 70-100 weight% in alkoxysilane is methyl trialkoxysilane as an organosiloxane resin composition which forms the 2nd layer excellent in especially abrasion resistance.

  The component (F) is a mixture such as a hydrolyzed part or all of alkoxysilane and a condensate obtained by condensing a part or all of the hydrolyzate, and these are obtained by causing a sol-gel reaction. Is.

The content of the component (E) and the component (F) in the organosiloxane resin composition depends on the stability of the organosiloxane resin composition, the transparency of the resulting cured film, the wear resistance, the scratch resistance, the adhesion and the cracks. It is determined from the point of occurrence. When the total of component (E) and component (F) is 100% by weight, the preferred mixing ratio of these two components is 10 to 60% by weight for component (E), and R ¹ mR ² nSiO ₍₄ ) for component (F). _{-mn) / 2} , 40 to 90% by weight, more preferably (E) component is 10 to 40% by weight, and (F) component is R ¹ mR ² nSiO _{(4-mn) / 2} 60 to 90% by weight.

The organosiloxane resin composition containing the component (E) and the component (F) can be prepared by performing a hydrolysis condensation reaction of alkoxysilane.
Water required for the hydrolysis reaction of alkoxysilane is supplied from this dispersion when a water-dispersed colloidal silica dispersion is used, and water may be added if necessary. Usually, 1 to 10 equivalents, preferably 1.5 to 7 equivalents of water is used per 1 equivalent of alkoxysilane.

  The hydrolysis-condensation reaction of alkoxysilane needs to be performed under acidic conditions, and an acid is generally used as a hydrolysis agent in order to perform hydrolysis under such conditions. Such an acid may be added in advance to the alkoxysilane or colloidal silica dispersion, or both may be added after mixing. Moreover, this addition can also be divided into 1 time or 2 times or more. Such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, paratoluene sulfone. Examples thereof include organic acids such as acids, and organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid and maleic acid are preferred, and acetic acid is particularly preferred from the viewpoint of ease of pH control. When an inorganic acid is used, it is preferably used at a concentration of 0.0001 to 2N, more preferably 0.001 to 0.1N. When an organic acid is used, it is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of alkoxysilane.

  The conditions for the hydrolytic condensation reaction cannot be unequivocally changed depending on the type of alkoxysilane used, the type and amount of colloidal silica coexisting in the system, but the system temperature is usually 20 to 70 ° C., reaction time 1 hour to several days. According to the above method, the 2nd layer which does not produce | generate precipitation and is more excellent in abrasion resistance can be obtained.

(Metal oxide (G))
The organosiloxane resin composition preferably contains a metal oxide (G). The weather resistance can be increased by the component (G). As the component (G), at least one metal oxide selected from the group consisting of titanium oxide, zinc oxide, cerium oxide, tin oxide, and tungsten oxide is preferably used with little decomposition by light. In particular, titanium oxide is preferably used. The content of the component (G) is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 5.0 parts by weight, based on 100 parts by weight of the total of the E component and the F component.

(Curing catalyst (I))
The organosiloxane resin composition preferably further contains a curing catalyst as component (I). Examples of the curing catalyst include lithium salts of aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, and succinic acid, alkali metal salts such as sodium salt and potassium salt, benzyltrimethylammonium salt, choline salt, Quaternary ammonium salts such as tetramethylammonium salt and tetraethylammonium salt can be mentioned. Specifically, sodium acetate, potassium acetate, choline acetate and benzyltrimethylammonium acetate are preferably used. The content of the curing catalyst (I) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to a total of 100 parts by weight of the component (E) and the component (F). is there.

(solvent)
The second layer is formed by applying an organosiloxane resin composition (paint) onto the first layer. The organosiloxane resin composition preferably contains a solvent.
As the solvent, it is necessary that the organosiloxane resin composition is stably dissolved. For this purpose, it is desirable to use a solvent in which at least 20% by weight, preferably 50% by weight or more is alcohol.

  Specific examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, and 4-methyl-2-pentanol. , 2-butoxyethanol and the like. Of these, low-boiling alcohols having 1 to 4 carbon atoms are preferable, and 1-butanol and 2-propanol are particularly preferable in terms of solubility, stability, and coatability.

  In the case of using water in the water-dispersed colloidal silica, water that does not participate in the hydrolysis reaction, lower alcohol generated by hydrolysis of alkoxysilane, and organic solvent-dispersed colloidal silica, the dispersion medium And an acid added to adjust the pH of the organosiloxane resin composition for coating.

  Acids used for pH adjustment include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid and other inorganic acids, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid Organic acids such as acid, lactic acid, and paratoluenesulfonic acid are mentioned. From the viewpoint of ease of pH control, organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are used. preferable.

  As other usable solvents, it is necessary to mix with water / alcohol, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, etc. Examples of the esters include ethers, ethyl acetate, n-butyl acetate, isobutyl acetate, and ethoxyethyl acetate.

  The content of the solvent is preferably 50 to 2000 parts by weight, more preferably 150 to 1400 parts by weight with respect to 100 parts by weight as a total of the component (E) and the component (F). The concentration of the solid content is preferably 5 to 70% by weight, more preferably 7 to 40% by weight.

  The organosiloxane resin composition preferably has a pH of 3.0 to 6.0, more preferably 4.0 to 5.5 by adjusting the contents of the acid and the curing catalyst. By adjusting the pH within this range, gelation of the organosiloxane resin composition at room temperature can be prevented, and storage stability can be increased. The organosiloxane resin composition usually becomes a stable coating material by further aging for several hours to several days.

In the organosiloxane resin composition, the components (E), (F) and (G) are dissolved and / or dispersed in a solvent, and (i) the weight of the component (F) is adjusted to R ¹ _m R ² _n SiO _{(4-mn ) / 2} , the total amount of the component (E) and the component (F) is 100% by weight, the component (E) is 10 to 60% by weight, and the component (F) is 40 to 90% by weight. And (G) component is 0.1 to 15 parts by weight with respect to 100 parts by weight of the total amount of component (E) and component (F), and (ii) laser diffraction particle size of component (G) When the cumulative 50% particle size and the cumulative 90% particle size in distribution measurement are D50 and D90, respectively, it is preferable that D90 is 100 nm or less and D90 / D50 is 20 or less.

  The metal oxide (G) is preferably titanium oxide, zinc oxide or cerium oxide. The metal oxide (G) is preferably obtained by dispersing a slurry in which a metal oxide is dispersed in water or an organic solvent using a medium mill filled with a medium having an average particle size of 100 μm or less. It is preferable that the concentration of the total amount of components (E), (F) and (G) is 5 to 70% by weight. The solvent preferably contains 50% by weight or more of an alcohol having 1 to 4 carbon atoms. Furthermore, it is preferable to contain 0.01-10 weight part of curing catalyst (I) with respect to 100 weight part of total amounts of (E) and (F) component.

  The second layer can be formed by applying an organosiloxane resin composition (coating material) on the first layer and then thermosetting. The second layer is preferably formed continuously following the formation of the first layer.

  As a coating method, a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method can be appropriately selected depending on the shape of the substrate to be coated. . After the organosiloxane resin composition is applied, the solvent is usually dried and removed at a temperature from room temperature to a temperature lower than the heat distortion temperature of the substrate, followed by thermosetting. The thermosetting is preferably performed at a high temperature within a range where there is no problem in the heat resistance of the base material because the curing can be completed earlier. At normal temperature, thermosetting does not proceed and a cured film cannot be obtained. This means that the organosiloxane in the paint is partially condensed. In the process of thermosetting, the remaining Si—OH undergoes a condensation reaction to form a Si—O—Si bond, resulting in a coat layer with excellent wear resistance.

  The thermosetting temperature is preferably 50 to 200 ° C, more preferably 80 to 160 ° C, and still more preferably 100 to 140 ° C. The heat curing time is preferably 10 minutes to 4 hours, more preferably 20 minutes to 3 hours, and further preferably 30 minutes to 2 hours.

  The thickness of the second layer is preferably 1 to 20 μm, more preferably 2 to 10 μm, and further preferably 3 to 8 μm. If the thickness of the second layer is within such a range, the second layer will not crack due to the stress generated during thermosetting, and the adhesion between the second layer and the first layer will not decrease. As a result, a second layer having sufficient wear resistance as an object of the present invention can be obtained.

<Plasma CVD film 80>
As the plasma CVD film 80, after the thermosetting acrylic resin film 60 and the organosiloxane resin thermosetting film 70 are laminated on the plastic substrate 50, for example, oxygen gas is used together with at least one kind of organosiloxane, organosilane, or silazane vapor. It is laminated on the surface of the organosiloxane resin thermosetting film 70 by being present and plasma polymerized. The thickness is desirably 3 to 10 μm, particularly 5 to 8 μm. If the film thickness is small, it is difficult to obtain desired hardness and scratch resistance. Conversely, if the thickness exceeds 10 μm, the effects of hardness and scratch resistance are saturated, which is not economical.

The plasma CVD film 80 preferably has a lower O / Si ratio on the organosiloxane resin thermosetting film 70 side than on the outer surface side. Further, the plasma CVD film 80 preferably has an O / Si ratio that increases from the contact surface with the organosiloxane resin thermosetting film 70 toward the surface. The O / Si ratio in the plasma CVD film 80 continuously increases from the interface with the organosiloxane resin thermosetting film 70 in the range of 0.1 to 1 μm, particularly toward the outer surface side of the plasma CVD film 80. It is best to do.

Thus, the O / Si ratio of the contact surface of the plasma CVD film 80 with the organosiloxane resin thermosetting film 70 continuously changes from the surface toward the contact surface with the organosiloxane resin thermosetting film 70. Alternatively, in the range of 0.1 to 1 μm from the interface, the O / Si ratio increases, so that the contact surface (interface) with the organosiloxane resin thermosetting film 70 in the plasma CVD film 80 and the vicinity of the wet surface Adhesiveness to the organosiloxane resin thermosetting film 70 is enhanced. On the other hand, by having an inclined zone and a flat zone while changing the O / Si ratio from the contact surface with the organosiloxane resin thermosetting film 70 toward the surface, the adhesion is ensured and the surface side is suitable for scratch resistance. Sex can be imparted.

  FIG. 2 schematically shows a state in which the chemical composition of the plasma CVD film 80 continuously changes. As shown in FIG. 2, the O / Si ratio becomes an inclined zone that increases from the vicinity of the surface of the organosiloxane resin thermosetting film 70 toward the surface, and a close contact surface is formed in this portion. Thereafter, the O / Si ratio is maintained at a constant ratio until reaching the surface of the plasma CVD film 80, and accordingly, the hardness is also maintained until reaching the surface of the plasma CVD film 80. ing.

  The plasma polymerization performed when forming the plasma CVD film 80 is low-temperature plasma polymerization, and is performed by a method known per se. That is, the apparatus for plasma polymerization (hereinafter referred to as “plasma polymerization apparatus”) may be any apparatus that excites organosilicon compound vapor and oxygen gas in the apparatus, and is usually used in plasma CVD (chemical vapor deposition). An apparatus can be used, and a capacitive coupling type apparatus is particularly preferably used.

  In the capacitively coupled plasma polymerization apparatus, both an external electrode system in which an RF (radio high-frequency, hereinafter the same) electrode is installed outside the vacuum reaction container and an internal electrode system in which the RF electrode is installed in the vacuum reaction container are used. Can be used. In order to excite organosilicon compound vapor and oxygen gas by plasma, a high frequency power source is used. The frequency may be any frequency specified as an industrial frequency band by the Radio Law, for example, 13.56 MHz. (MHz), 27.12 MHz, 40.68 MHz, 2.45 gigahertz (GHz), 5.8 GHz, 22.125 GHz, and 10 kilohertz (KHz) or less are available, but 13.56 MHz is particularly preferred. Used for.

  The power input to the RF power source (hereinafter also referred to as input RF power or input power) varies depending on the type of organosilicon compound used and the scale of the plasma polymerization apparatus, and cannot be specified. , About 50-5000W.

When the input power is changed with time, the ratio of changing the input power with respect to the unit time (hereinafter also referred to as input power gradient) is kept substantially constant, but does not prevent the change. Therefore, this input power gradient is determined by the types of plastic substrates, the types of organosilicon compounds, the ratio of these when two or more types of organosilicon compounds are used, the ratio of oxygen to the organosilicon compounds, and the desired adhesion. However, it is generally preferable to be about 10 to 500 W / min. Further, the degree of vacuum at the time of forming a film in the vacuum reaction vessel is usually 20 Pa or less, and practically, preferably about 10 to 1 × 10 ⁻² Pa. Furthermore, when the base material is installed in a vacuum reaction vessel and a film is formed, before introducing the raw material gas for film formation, the pressure in the vacuum reaction vessel is lowered to the time when the above film is formed, The properties (adhesion, etc.) of the formed film are improved.

  When plasma polymerization is performed under such conditions, since this plasma polymerization is a low temperature plasma, there is substantially no heat generation in the vacuum reactor of the plasma device, but the power frequency for plasma generation and the input power Depending on the case, the temperature may exceed the softening point of the plastic substrate. In this case, a structure for cooling the substrate may be added. Further, the treatment time varies depending on the kind of the organosilicon compound, the ratio between the organosilicon compound and oxygen, the conditions for the plasma polymerization, and the like, and cannot be specified in general. However, in practice, it may normally be about 5 to 60 minutes. .

In the present invention, it is desirable to use a silicon compound containing a carbon atom or a silicon compound containing a carbon atom and an oxygen atom or a nitrogen atom as the organosilicon compound.
Specific compounds include, for example, tetramethoxysilane, vinyltrimethoxysilane, octamethylcyclotetrasiloxane, tetraethoxysilane, hexamethylcyclotrisiloxane, octamethyltrisiloxane, hexamethyldisiloxane, hexamethyldisiloxane, hexaethyldisiloxane. Siloxane, hexaethylcyclotrisiloxane, tetramethylsilane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetramethyldisilazane, pentamethyldisiloxane, hexamethyldisilazane, heptamethyl Disilazane, 1,3-dimethoxytetramethyldisiloxane, 1,3-diethoxytetramethyldisiloxane, hexamethylcyclotrisilazane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1, 1, , 3,5,5,5-heptamethyltrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,3,5,5,7,7-octamethylcyclotetrasilazane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (trimethylsiloxy) silane, decamethyltetrasiloxane, etc. .

  These organosilicon compounds can be used alone, but two or more of them can be used together, and an organic silicon compound for improving scratch resistance and an organic for improving adhesion By using one or more types of silicon compounds in combination, both the scratch resistance of the coating and the adhesion to the surface of the plastic substrate may be increased.

  These organosilicon compounds are used with oxygen gas. Further, the organosilicon compound and oxygen gas may be mixed and supplied in advance to the vacuum reaction vessel of the plasma polymerization apparatus, or separately supplied to this vacuum reaction vessel and mixed with each other in the vacuum reaction vessel. It can also be made. The organosilicon compound is usually supplied as a gas, but can be supplied as a liquid. Oxygen is usually supplied as a gas.

  The ratio of oxygen to the organosilicon compound differs depending on the type of organosilicon compound used and the desired hardness of the coating, and cannot be specified unconditionally. However, in general, the ratio of the amount of oxygen to the amount of the organosilicon compound is determined. As it increases, it tends to decrease the carbon ratio in the coating, thereby hardening the coating formed on the surface of the plastic substrate and increasing the scratch resistance. It is appropriately selected from the range of about 10 to 500 times volume in the standard state with respect to the steam.

  As described above, in the plasma CVD film 80, when the silicon content of the organosiloxane resin thermosetting film 70 is high, the silicon content decreases from the contact surface with the organosiloxane resin thermosetting film 70 toward the surface. It is desirable to be damned. In this case, the change of the content rate may be continuous or stepwise. In any case, in order to form the plasma CVD film 80 showing the gradient of the content rate, for example, (1) only the input RF power for generating plasma excitation is continuously changed over time. (2) The input RF power for generating plasma excitation is continuously changed over time, and the vapor and / or oxygen gas supply rates of one or more organic silicon compounds are continuously changed over time. It is possible to adopt a method such as changing it automatically.

  FIG. 3 and FIG. 4 schematically illustrate specific modes of change over time in the reaction conditions in the plasma polymerization reaction for forming the plasma CVD film 80 according to the present invention. In FIG. 3, the supply rate of oxygen gas and organosilicon compound vapor is continuously increased over time, and the ratio of oxygen gas and organosilicon compound vapor is continuously changed over time. Along with this, the input RF power is also continuously reduced with the passage of time. After a certain period of time, the supply rate of oxygen gas and organosilicon compound vapor and the input RF power are kept constant.

  Here, although not shown in the figure, when two types of organosilicon compounds are used in combination, the sum of the organosilicon compound 1 and the organosilicon compound 2 may be kept constant, and this sum may be used for time. You may change continuously with progress of. Thus, for example, only one organosilicon compound can be used in the first half of the plasma polymerization and only the other organosilicon compound can be used in the second half of the plasma polymerization.

  Thus, in the plasma polymerization, the surface of the organosiloxane resin thermosetting film 70 is reduced by continuously reducing the input RF power and continuously changing the supply rate of the organosilicon compound and / or the supply rate of oxygen. And the plasma CVD film 80, which is hard and has high scratch resistance, are firmly attached to each other.

  FIG. 5 shows an example of a plasma polymerization apparatus which is an apparatus for forming a plasma CVD film 80 according to the present invention. In the illustrated example, the first electrode 10, the second electrode 20, and the processing substrate 30 are arranged in the vertical direction, but it is understood that the effect of the present invention is substantially the same even if they are juxtaposed in the horizontal direction. , Refuse in advance.

  In the plasma processing apparatus in the present example, a first electrode (cathode electrode) 10 and a second electrode (anode electrode) 20 are arranged facing the inside of the vacuum vessel 1. A plastic processing substrate 30 is disposed on the surface of the first electrode 10 and supported by an appropriate holder. The inside of the vacuum vessel 1 is depressurized by the vacuum pump 5, and while introducing the reaction gas 7 from the outside into the vacuum vessel 1, plasma of the reaction gas is supplied to the first electrode (cathode electrode) 10 and the second electrode ( And an anode electrode) 20. The second electrode (anode electrode) 20 is grounded.

  Patent Documents disclosed by the present applicants regarding a method of directly forming a plasma CVD film on a plastic resin substrate without forming an acrylic resin thermosetting film and an organosiloxane resin thermosetting film according to the present invention The film forming method listed in 3 is suitable.

However, if a plasma CVD film is formed on the surface on which the acrylic resin thermosetting film and the organosiloxane resin thermosetting film are formed according to the same method, the adhesion to the resin substrate is poor. Therefore, in order to obtain a plastic laminate exhibiting sufficient hardness and scratch resistance while improving adhesion to the substrate, intensive studies and various experiments were tried.
One example is shown below as an example and a comparative example. The part in an Example means a weight part.

The obtained plastic laminate was evaluated by the following method.
(1) Appearance evaluation: The presence or absence of a coat layer appearance (crack) of the test piece was visually confirmed.
(2) Adhesiveness: 100 grids with a 1 mm interval are made on the coat layer with a cutter knife, Nichiban adhesive tape (trade name “Serotape (registered trademark)”) is pressure-bonded, and peeled strongly and vertically. It was evaluated by the number of grids remaining above. (Conforms to JISK5400)
For example, 100 (3) indicates that the test was performed three times and 100 grids remained. 95 (1) represents that 95 grids remained in the first test.
(3) Abrasion resistance: One surface of the double-sided coating layer was worn with a wear wheel of CS-10F manufactured by Calibrase, and the surface of the 25 rotation wear wheel was polished with a S-11 abrasive paper manufactured by Calibrase before the test. A 1000-rotor Taber abrasion test was conducted, and the difference ΔH between the haze after the Taber abrasion test and the haze before the Taber abrasion test was measured and evaluated (according to ASTM D1044). (Haze = Td / Tt × 100, Td: scattered light transmittance, Tt: total light transmittance)
(4) Scratch resistance: One surface of the double-sided coating layer of the test piece was rubbed with # 0000 steel wool, and then the scratched state of the surface was visually evaluated in five stages.
1: No damage even when rubbed 10 times at 500 g load 2: Slightly damaged when rubbed 10 times at 500 g load 3: Slightly damaged when rubbed 10 times at 500 g load 4: Damaged when rubbed 10 times at 500 g load 5: 100 g load (5) Boiling water resistance: The appearance change and adhesion of the coating layer after the test piece was immersed in boiling water for 2 hours were evaluated.
(6) Heat resistance: The test piece was held at 110 ° C. in a thermostatic bath, and the appearance change and adhesion of the coat layer after 1000 hours were evaluated.

(Plastic substrate)
A polycarbonate resin plate was used as a transparent plastic substrate.
First, the preparation method of the material liquid used for the acrylic resin thermosetting film and the organosiloxane resin thermosetting film is shown below.
[Method of preparing material solution]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 97 parts of ethyl methacrylate, 19.5 parts of 2-hydroxyethyl methacrylate, 0.18 parts of azobisisobutyronitrile and 200 parts of 1,2-dimethoxyethane were added. Add, mix and dissolve. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 80 parts of a copolymer (acrylic resin (A)) having an EMA / HEMA composition ratio of 85/15 (molar ratio). The copolymer had a hydroxyl value of 72.1 mg KOH / g and a weight average molecular weight of 80,000 in terms of polystyrene.

  5.8 parts of the acrylic resin (A) and 1.5 parts of 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole are mixed with 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone, 24 parts of isopropanol, and 1- Dissolve in a mixed solvent consisting of 3.2 parts of methoxy-2-propanol, and then add “VESTANATB 1358/100” (1 equivalent to 1 equivalent of isocyanate group to 1 equivalent of hydroxy group of the acrylic resin (A) in this solution. 2.7 parts of Degussa Japan polyisocyanate compound precursor) and 0.001 part of di-n-butyltin dilaurate were added and stirred at 25 ° C. for 5 minutes to prepare an acrylic resin film composition (I).

  208 parts of tetraethoxysilane and 81 parts of 0.01 mol / l hydrochloric acid were mixed with ice water while cooling. This mixed solution was stirred at 25 ° C. for 3 hours and diluted with 11 parts of isopropanol to obtain 300 parts of a tetraethoxysilane hydrolysis condensate solution (S2).

[Example 1]
Acidic water dispersion type colloidal silica dispersion (Nissan Chemical Industry Co., Ltd. “Snowtex O40” solid content concentration 40 wt%) 25 parts, water 8 parts 3 parts acetic acid 3 parts and stirred, this dispersion liquid ice bath To 50 parts of methyltrimethoxysilane under cooling. The mixture was stirred at 25 ° C. for 1 hour and a half, and then the reaction solution stirred at 70 ° C. for 2 hours was cooled with ice water. To this, 0.4 part of 45% choline methanol solution as a curing catalyst was mixed under ice water cooling, Dilution with 20 parts of isobutanol, 20 parts of methyl ethyl ketone, and 10 parts of ethyl acetate gave a coating composition (i) for the second layer.

  The coating composition is coated on a transparent polycarbonate substrate having a thickness of 2 mm, which is preliminarily coated on both sides of the acrylic resin film composition (I) by dip coating so as to have a cured film thickness of 4 μm and thermally cured at 120 ° C. for 1 hour. (I) was coated on both sides by dip coating so as to have a cured film thickness of 5 μm, and thermally cured at 120 ° C. for 1 hour to obtain a transparent polycarbonate laminate having a coating layer.

  A plasma CVD layer was laminated on a plastic formed body having an acrylic resin thermosetting film and an organosiloxane resin thermosetting film on the obtained polycarbonate substrate. Using the configuration of the capacitively coupled internal electrode type plasma polymerization apparatus shown in FIG. 5, film formation is performed by changing the film formation conditions of the organosilicon compound flow rate, oxygen gas flow rate, and high frequency power as shown in FIG. It was. 1,3,5,7-tetramethylcyclotetrasiloxane is used as the organosilicon compound, and the high-frequency power is changed from 3000 to 1000 W while changing the flow rate from 3 to 30 sccm and the oxygen flow rate from 25 to 1000 sccm. To form a film. The pressure in the chamber at this time was 0.5 → 10 Pa. The thickness of the obtained plasma CVD film was 5 μm. The tilt zone thickness was 1 μm, and the flat zone O / Si ratio was 1.5. Table 2 shows the results of evaluation of the polycarbonate laminate having the obtained coating layer.

[Example 2]
In the same manner as in Example 1, an acrylic resin thermosetting film and an organosiloxane resin thermosetting film were formed on a polycarbonate substrate.
A plasma CVD layer was laminated on a plastic molded body having an acrylic resin thermosetting film and an organosiloxane resin thermosetting film on the obtained polycarbonate substrate. Using the configuration of the capacitively coupled internal electrode type plasma polymerization apparatus shown in FIG. 5, film formation is performed by changing the film formation conditions of the organosilicon compound flow rate, oxygen gas flow rate, and high frequency power as shown in FIG. It was. 1,3,5,7-tetramethylcyclotetrasiloxane is used as the organosilicon compound, and the high frequency power is changed from 3000 to 1100 W while changing the flow rate from 2 to 30 sccm and the oxygen flow rate from 25 to 1000 sccm. To form a film. The pressure in the chamber at this time was 0.5 → 10 Pa. The thickness of the obtained plasma CVD film was 7 μm. The tilt zone thickness was 1 μm, and the flat zone O / Si ratio was 1.4. Table 2 shows the results of evaluation of the polycarbonate laminate having the obtained coating layer.

[Comparative Example 1]
A polycarbonate resin plate was used as a transparent plastic substrate.
In the same manner as in Example 1, an acrylic resin thermosetting film and an organosiloxane resin thermosetting film were formed on a polycarbonate substrate.

  Next, using the capacitively coupled internal electrode type plasma polymerization apparatus shown in FIG. 5, the supply rate of the organosilicon compound vapor and the oxygen gas is continuously increased over time as shown in FIG. On the other hand, plasma polymerization was carried out by continuously increasing the input RF power with the passage of time, and a hard coating was formed on the surface of the plastic substrate.

  As the organosilicon compound, 1,3,5,7-tetramethylcyclotetrasiloxane is used, the flow rate is changed from 2 to 30 sccm, and the oxygen flow rate is changed from 40 to 1000 sccm, while the high frequency power is changed from 50 to 1200 W. A film was formed. The pressure in the chamber at this time was 0.5 → 10 Pa. The thickness of the obtained plasma CVD film was 7 μm. The tilt zone at this time had a composition having a tilt opposite to that of Example 1, the tilt zone thickness was 3 μm, and the O / Si ratio of the flat zone was 1.5.

[Comparative Example 2]
A polycarbonate resin plate was used as a transparent plastic substrate.
In the same manner as in Example 1, an acrylic resin thermosetting film and an organosiloxane resin thermosetting film were formed on a polycarbonate substrate.

  Next, using the capacitively coupled internal electrode type plasma polymerization apparatus shown in FIG. 5, the supply rate of the organosilicon compound vapor and the supply rate of oxygen gas are kept constant as shown in FIG. Plasma polymerization was performed while keeping the input RF power constant, and a hard film was formed on the surface of the plastic substrate.

  As the organosilicon compound, 1,3,5,7-tetramethylcyclotetrasiloxane was used, and the film was formed while maintaining the high-frequency power at 1200 W while maintaining the flow rate at 30 sccm and the oxygen flow rate at 1000 sccm. . The pressure in the chamber at this time was 10 Pa. The thickness of the obtained plasma CVD film was 5 μm. In this case, there was no inclined zone and the O / Si ratio of the flat zone was 1.8.

[Comparative Example 3]
In the same manner as in Example 1, an acrylic resin thermosetting film and an organosiloxane resin thermosetting film were formed on a polycarbonate substrate.
A plasma CVD layer was laminated on a plastic molded body having an acrylic resin thermosetting film and an organosiloxane resin thermosetting film on the obtained polycarbonate substrate. Using the configuration of the capacitively coupled internal electrode type plasma polymerization apparatus shown in FIG. 5, film formation is performed by changing the film formation conditions of the organosilicon compound flow rate, oxygen gas flow rate, and high frequency power as shown in FIG. It was. 1,3,5,7-tetramethylcyclotetrasiloxane is used as the organosilicon compound, and the high frequency power is changed from 3000 to 1100 W while changing the flow rate from 2 to 30 sccm and the oxygen flow rate from 25 to 1000 sccm. To form a film. The pressure in the chamber at this time was 0.5 → 10 Pa. The conditions were almost the same as in Example 2, but the points at which the organosilicon compound flow rate, oxygen flow rate, and high-frequency power were changed were shifted in time from Example 2 and adjusted so that the sloped zone was 2.5 μm. . The thickness of the obtained plasma CVD film was 7 μm. The O / Si ratio of the flat zone at this time was 1.5. Table 2 shows the results of evaluation of the polycarbonate laminate having the obtained coating layer.

[Comparative Example 4]
A polycarbonate resin plate was used as a transparent plastic substrate, and an acrylic resin thermosetting film and an organosiloxane resin thermosetting film were laminated thereon by the method described in Example 1. In this example, a plasma CVD film was not formed, and a two-layer structure of an acrylic resin thermosetting film and an organosiloxane resin thermosetting film was used. The results of evaluating the polycarbonate laminate obtained here are shown in Table 2.

  When attention is paid to the results in Table 2, it can be seen from Examples 1 and 2 that the plasma CVD film has excellent adhesion from the comparison with Comparative Example 1. In addition, the numerical value of wear resistance is greatly improved as compared with Comparative Example 4, and therefore, it is clear that the hardness against scratches caused by wipers and the like particularly when used for windows is drastically improved. I understand. In Comparative Example 2, there is no inclined zone, and Comparative Example 3 shows the result of thickening the inclined zone. However, both of them were boiling water resistant and heat resistant, and inferior to Examples 1 and 2.

  From the above results, it was confirmed that while using a capacitively coupled internal electrode type plasma polymerization apparatus, the supply rate of oxygen gas and organosilicon compound vapor was continuously increased over time, while the input RF power was The plasma CVD film laminated on the thermosetting film of the organosiloxane resin by performing plasma polymerization while continuously reducing the input power over time is excellent in scratch resistance and adhesion. I understand.

DESCRIPTION OF SYMBOLS 50 ... Plastic substrate, 60 ... Acrylic resin thermosetting film, 70 ... Organosiloxane resin thermosetting film, 80 ... Plasma CVD film, 100 ... Transparent or translucent plastic laminated body

Claims (5)

Acrylic resin thermosetting film, organosiloxane resin thermosetting film and organosilicon compound plasma CVD film are sequentially laminated on at least one surface of a plastic substrate,
The CVD film has an inclined zone in which the abundance ratio (O / Si ratio) between oxygen atoms and silicon atoms increases from the interface with the thermosetting film of the organosiloxane resin, followed by a substantially constant flat zone. Ri consists of,
A plastic laminate having a thickness of an inclined zone of the CVD film of 0.1 to 1 μm . The plastic laminate according to claim 1, wherein the flat zone of the CVD film has an O / Si ratio of 1.4 or more and less than 2. The CVD film is a film obtained by plasma polymerization in the presence of vapor and oxygen gas of at least one organic silicon compound selected from the group consisting of compounds consisting of organosiloxane, organosilane and silazane. 3. The plastic laminate according to 1 or 2 . The plastic laminate according to any one of claims 1 to 3 , wherein the plastic substrate is a transparent or translucent resin. At least on one side of a plastic substrate, a step of wet-coating acrylic resin and thermosetting, a step of wet-coating organosiloxane resin and thermosetting, and at least selected from the group consisting of compounds consisting of organosiloxane, organosilane and silazane Including the step of forming a film by plasma polymerization in the presence of vapor of one kind of organosilicon compound and oxygen gas in the coexistence,
The plasma polymerization comprising an inclined zone in which an abundance ratio of oxygen atoms to silicon atoms (O / Si ratio) increases gradually from the interface with the thermosetting film of the organosiloxane resin, followed by a substantially constant flat zone. Produce a membrane ,
Method for producing a plastic laminate according to claim 0.1~1μm and to Rukoto the thickness of the inclined zone of the CVD film.

Images